Polymer latex binders useful in zero or low VOC coating compositions

ABSTRACT

Polymer latex binders useful for preparing coating compositions containing low levels of, or which are substantially free of, volatile organic compounds (VOCs) such as volatile freeze-thaw additives are prepared by multistage emulsion polymerization, wherein one stage provides a copolymer having a relatively high glass transition temperature and containing an oxyalkylene-containing (meth)acrylate comonomer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 14/376,683, filed Aug. 5, 2014, which is a national stageapplication under 35 U.S.C. §371 of PCT/US2013/24700, filed Feb. 5,2013, which claims benefit to U.S. patent application 61/597,438 filedon Feb. 10, 2012

FIELD OF THE INVENTION

The present invention relates to polymer latex binders useful forpreparing coating compositions containing low levels of, or which aresubstantially free of, volatile organic compounds (VOCs) such asvolatile freeze-thaw additives, as well as to methods of preparing suchpolymer latex binders and coating compositions.

BACKGROUND OF THE INVENTION

Latex coating compositions are utilized for a variety of applications,including, for example, as paints for various types of surfaces.However, such compositions are recognized as being potentially unstablewhen exposed to freeze-thaw cycles. That is, repeated freezing andwarming of latex coating compositions can frequently lead todestabilization of the dispersed polymer in the latex (causing gelformation, for example). This, of course, is a significant problem sincethese coating compositions are expected to be exposed to a wide range oftemperatures during shipment and storage. For this reason, variousfreeze-thaw additives have been formulated into latex coatingcompositions in order to improve their resistance to such temperaturecycles. Traditionally, these additives have included relatively lowmolecular weight compounds such as alcohols, glycols and the like.

In recent years, however, such low molecular weight freeze-thawadditives have come under scrutiny since many are classified as volatileorganic compounds (VOCs). Environmental regulations in many locationslimit the level of VOCs that can be present in coating compositions. Forthis reason, there has been an effort to develop various newformulations that qualify as zero or low VOC yet still meet thefreeze-thaw stability requirements expected in the industry.

SUMMARY OF THE INVENTION

The present invention provides a multiphase emulsion polymer comprisingat least one hard phase polymer having a glass transition temperature offrom 0 to 100° C. and at least one soft phase polymer having a glasstransition temperature of less than 0° C. and at least 20° C. lower thanthe glass transition temperature of the hard phase polymer, wherein thehard phase polymer is a copolymer of at least one ethylenicallyunsaturated monomer and at least one oxyalkylene-containing(meth)acrylate corresponding to formula (I) or (II) or a mixturethereof:CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—R²;  (I)CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—P(═O)(OY)₂;  (II)wherein R¹ is H or CH₃, R² is H or a C₁-C₈ alkyl group, each X isindependently —(CH₂)₂—,—CH₂CH(CH₃)— or —CH(CH₃)CH₂—, each Y is independently H, ammonium or analkali metal atom, and n is an integer of from 1 to 30. Such multistageemulsion polymers are useful in the formulation of latex coatingcompositions which have a low or zero VOC content and yet have goodfreeze-thaw stability. Latex coating compositions including themultistage emulsion polymers of the present invention are also capableof exhibiting low temperature film-formability and block resistance.

In another aspect of the invention, a polymer latex binder useful in azero or low VOC latex coating composition is provided which comprisesthe afore-mentioned multiphase emulsion polymer in the form of latexparticles, water, and at least one emulsifier.

A zero or low VOC latex coating composition is provided in anotheraspect of the invention, comprising the aforementioned polymer latexbinder and at least one pigment.

The invention also provides a method of making a polymer latex binder,comprising:

-   -   (a) copolymerizing an aqueous emulsion of at least one        ethylenically unsaturated monomer and at least one        oxyalkylene-containing (meth)acrylate corresponding to        formula (I) or (II) or a mixture thereof:        CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—R²;  (I)        CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—P(═O)(OY)₂;  (II)        -   wherein R¹ is H or CH₃, R² is H or a C₁-C₈ alkyl group, each            X is independently        -   —(CH₂)₂—, —CH₂CH(CH₃)— or —CH(CH₃)CH₂—, each Y is            independently H, ammonium or an alkali metal atom, and n is            an integer of from 1 to 30, to form a hard phase polymer            having a glass transition temperature of from 0 to 100° C.;    -   (b) polymerizing one or more additional monomers in the presence        of the hard phase polymer to form a soft phase polymer;    -   wherein the hard phase polymer has a glass transition        temperature of from 0 to 100° C. and the soft phase polymer has        a glass transition temperature of less than 0° C. and at least        20° C. lower than the glass transition temperature of the hard        phase polymer.

The present invention further provides a multiphase emulsion polymercomprising at least two polymer domains prepared via a multistageemulsion polymerization in which subsequent stage polymerizations occurin the presence of the first and succeeding stage and in which one ofthe polymer domains comprises a hard phase polymer having a glasstransition temperature of from 0 to 100° C. and another of the polymerdomains comprises a soft phase polymer having a glass transitiontemperature of less than 0° C. and at least 20° C. lower than the glasstransition temperature of the hard phase polymer, wherein the hard phasepolymer is a copolymer of at least one ethylenically unsaturated monomerand at least one oxyalkylene-containing (meth)acrylate corresponding toformula (I) or (II) or a mixture thereof:CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—R²;  (I)CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—P(═O)(OY)₂;  (II)

wherein R¹ is H or CH₃, R² is H or a C₁-C₈ alkyl group, each X isindependently

—(CH₂)₂—, —CH₂CH(CH₃)— or —CH(CH₃)CH₂—, each Y is independently H,ammonium or an alkali metal atom, and n is an integer of from 1 to 30.

DETAILED DESCRIPTION OF THE INVENTION

The polymer particles of the latex of this invention may becharacterized as multi-stage polymers having a soft (low Tg) polymerphase (domain) and a hard (high Tg) polymer phase (domain), which areprepared via a multi-stage emulsion polymerization in which subsequentstage polymerizations occur in the presence of the first and succeedingstage polymer phases. Generally, the polymerizations are two-stagepolymerizations in which either stage can produce the soft or hardpolymer phase. In one desirable embodiment of the invention, the hardpolymer phase is formed first, followed by the soft polymer phase. Asmeasured by standard differential scanning calorimetric methods, thesoft polymer phase may, for example, have a Tg in the range of 0 to −70°C. and the hard polymer phase may, for example, have a Tg in the rangeof 0 to 100° C. or 10 to 90° C. (inclusive). In one embodiment of theinvention, there will be a difference in the Tg values between the twophases of 20 to 100° C.

In one embodiment of the invention, the soft polymer phase is an inner(core) phase within the polymer particles and the hard polymer phase isan outer (shell) phase.

The size of the polymer particles can vary. However, in variousdesirable embodiments of the invention, the particles have an averagediameter of less than 350 nm, or less than 300 nm, or less than 250 nm,or less than 200 nm, or less than 100 nm (inclusive). Particle size andparticle size distribution may be analyzed using Nanotrac UPA 150 (fromMicrotrac Inc.) to provide volume-averaged particle sizes based ondynamic light scattering techniques.

The soft polymer phase may, in various embodiments of the invention,represent from 90% to 40% by weight, or from 80% to 50% by weight, ofthe total polymer present in the polymer particles (inclusive). The hardpolymer phase may represent from 10% to 60% by weight, from 20% to 50%by weight, of the total polymer present in the polymer particles(inclusive). In one embodiment, the total of the weight % of the softpolymer phase and the weight % of the hard polymer phase is 100%.

The soft polymer phase may be prepared either as a homopolymer or as acopolymer from ethylenically unsaturated monomers (e.g., vinyl or(meth)acrylic containing monomers or other monomers containingpolymerizable carbon-carbon double bonds). The hard polymer phase, aswill be explained in more detail subsequently, is a copolymer of atleast one oxyalkylene-containing monomer and at least one additionalmonomer (other than an oxyalkylene-containing monomer) which is anethylenically unsaturated monomer such as a vinyl- or(meth)acrylic-containing monomer. The particular choice of monomers foreither phase will depend, among other considerations, on the desired Tgvalue for the phase. The glass transition temperatures of the polymerphases can be calculated using the Fox equation:1/Tg(polymer)=W(a)/Tg(a)+W(b)/Tg(b)+ . . . ,where W(a) and W(b) are the weight fractions of comonomers (a) and (b)and Tg(a) and Tg(b) are the glass transition temperatures forhomopolymers (a) and (b), respectively. Glass transition temperaturesfor various homopolymers are available in many literature sources,including J. Brandup and E. H. Immergut, Polymer Handbook, 2nd ed., JohnWiley & Sons, New York, pp 139-192 (1975).

Suitable examples of ethylenically unsaturated monomers include vinyl-and (meth)acrylic-containing monomers such as the alkyl esters (inparticular, the C1-C18 alkyl esters, where the alkyl group is linear orbranched) of acrylic and methacrylic acid such as methyl(meth)acrylate,ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate,n-butyl(meth)acrylate, isobutyl(meth)acrylate, pentyl(meth)acrylate,2-ethylhexyl(meth)acrylate, decyl (meth)acrylate, dodecyl(meth)acrylate, and stearyl (meth)acrylate; halo- andhydroxyl-substituted alkyl esters of (meth)acrylic acid such asα-chloroethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2- and3-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl (meth)acrylate; vinylesters of linear and branched carboxylic acids having 1 to 25 carbonatoms, preferably 2 to 20 carbon atoms, such as vinyl acetate, vinylpropionate, vinyl butyrate, vinyl valerate, vinyl 2-ethylhexylacrylate,vinyl isononanoate, vinyl laurate, vinyl stearate, vinyl versatate;styrene and styrene derivatives, such as alpha-methylstyrene,2-chlorostyrene, 4-chlorostyrene, 2,5-dichlorostyrene and4-methoxystyrene; as well as polymerizable unsaturated carboxylic acidssuch as unsaturated C3-C6 monocarboxylic acids, e.g., methacrylic acid,acrylic acid, and crotonic acid, monoesters of unsaturated C4-C6dicarboxylic acids such as mono-methylmaleate and mono-ethylmaleate, andunsaturated C4-C6 dicarboxylic acids, such as fumaric acid, maleic acid,and itaconic acid. Other examples of suitable monomers include(meth)acrylonitrile; cycloalkyl (meth)acrylates such ascyclohexyl(meth)acrylate; aryl and alkaryl esters of (meth)acrylic acidsuch as phenyl (meth)acrylate; acetoacetate moiety containing monomerssuch as 2-acetoacetoxyethyl (meth)acrylate, 3-acetoacetoxypropyl(meth)acrylate, 4-acetoacetoxybutyl (meth)acrylate, 2-cyanoacetoxyethyl(meth)acrylate, 3-cyanoacetoxypropyl (meth)acrylate, 4-cyanoacetoxybutyl(meth)acrylate, N-(2-acetoacetoxyethyl) (meth)acrylamide, allylacetoacetate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, and vinylacetoacetate; amide group-containing monomers such as (meth)acrylamide,diacetone acrylamide and maleinamide; epoxy group-containing monomerssuch as glycidyl (meth)acrylate and allylglycidyl ether; vinyl chloride;olefins such as ethylene; dienes such as butadiene, and the like.

In order to enhance the wet adhesion of the ultimate latex coatingcomposition, either one or the other, or both the soft phase polymer orthe hard phase polymer, may comprise a wet adhesion monomer, or acombination of wet adhesion monomers. These monomers are well known inthe art and include ethylenically unsaturated amino-, urea- andureido-functionalized monomers such as aminoethyl acrylate andmethacrylate, dimethylaminopropyl acrylate and methacrylate,3-dimethylamino-2,2-dimethylpropyl-1-acrylate and methacrylate,2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethylacrylate and methacrylate, N-(3-dimethylaminopropyl) acrylamide andmethacrylamide, N-(3-dimethylamino-2,2-dimethylpropyl) acrylamide andmethacrylamide, N-dimethylaminomethyl acrylamide and methacrylamide,N-dimethylaminomethyl acrylamide and methacrylamide,N-(4-morpholino-methyl) acrylamide and methacrylamide, vinylimidazole,vinylpyrrolidone, N-(2-methacryloyloxyethyl) ethylene urea,N-(2-methacryloxyacetamidoethyl)-N,N′-ethyleneurea, allylalkyl ethyleneurea, N-methacrylamidomethyl urea, N-methacryoyl urea, 2-(1-imidazolyl)ethyl methacrylate, N-(methacrylamido)ethyl ethylene urea (Sipomer WAMII, Rhodia) and allyl ureido wet adhesion monomer (Sipomer WAM, Rhodia).The wet adhesion monomers may, for example, be present in the soft orhard phase polymer in an amount from 0.2% to 2.0% by weight of the totalpolymer.

To reduce mixing between the two polymer phases and improve the blockresistance of the coating formulations, either or both of the phases maycomprise a low level of a multifunctional crosslinking monomer havingtwo or more polymerizable carbon-carbon double bonds per molecule, suchas vinyl or allyl acrylate or methacrylate, divinyl benzene, diallylmaleate, multifunctional acrylates and methacrylates, andmethylene-bis-acrylamide. The multifunctional monomer may be present inan amount from 0.01% to 5% by weight of the total polymer.

When either or both of the polymers constituting the phases comprise oneor more carbonyl-containing monomers (such as a monomer bearing anacetoacetate functionality), crosslinking reactions involving thesemonomers may be achieved by adding carbonyl-reactive crosslinking agentsor compounds to the polymer. Examples of carbonyl-reactive compoundsinclude polyfunctional amines, hydrazine, alkyl dihydrazines, alkylenedioxime ethers, and dihydrazides of dicarboxylic acids. Crosslinking ofthe polymers may take place during drying of a film of the latex coatingcomposition.

Chain transfer agents including mercaptans, polymercaptans, alcohols,and halogen compounds may, if so desired, be used in the polymerizationmixture in order to moderate the molecular weight of the polymer. Chaintransfer agents may be used in either stage of the two stagepolymerization.

The hard phase polymer is a copolymer of an ethylenically unsaturatedmonomer (such as any of the vinyl- and acrylic-containing monomerspreviously mentioned, including mixtures thereof) and a secondethylenically unsaturated monomer which contains an acrylate ormethacrylate group as well as one or more oxyalkylene groups permolecule such as oxyethylene and/or oxypropylene groups. Theoxyalkylene-containing (meth)acrylate may correspond to formula (I) or(II):CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—R²;  (I)CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—P(═O)(OY)₂;  (II)wherein R¹ is H or CH₃, R² is H or a C₁-C₈ alkyl group (e.g., methyl,ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, etc.), each X isindependently —(CH₂)₂—, —CH₂CH(CH₃)— or —CH(CH₃)CH₂—, each Y isindependently H, ammonium or an alkali metal atom (e.g., Na, K), and nis an integer of from 1 to 30 (or 2 to 25 or 3 to 20). Mixtures ofdifferent oxyalkylene-containing (meth)acrylates may be utilized.

The oxyalkylene-containing (meth)acrylate thus may be a polyethyleneglycol mono(meth)acrylate and/or a phosphate ester of a polyethyleneglycol mono(meth)acrylate. Such monomers are well known in the art andmay be readily obtained from commercial sources. For example, thephosphate esters of polyethylene glycol mono(methacrylate) sold byRhodia under the trade name Sipomer® PAM may be utilized. Monomerscorresponding to Formula (I) may be prepared by reacting epoxides suchas ethylene oxide and/or propylene oxide with (meth)acrylic acid andthen optionally reacting the terminal hydroxyl group to form an alkylether group. It is understood that monomers prepared by such a methodmay be mixtures of compounds having different n values.

The amount of the oxyalkylene-containing (meth)acrylate in the copolymerof the hard polymer phase may be varied as needed to achieve the desiredcombination of properties in the final latex coating composition whichis formulated using the multistage emulsion polymer. For example, anamount of oxyalkylene-containing (meth)acrylate may be incorporatedwhich is effective to improve the freeze thaw stability of the latexcoating composition as compared to a latex coating composition preparedusing an analogous multistage emulsion polymer where the hard phasepolymer does not contain any oxyalkylene-containing (meth)acrylate. Atthe same time, however, the use of excessive proportions of theoxyalkylene-containing (meth)acrylate should be avoided; for example,the desired Tg value for the hard polymer phase may be challenging toachieve if a relatively high amount of oxyalkylene-containing(meth)acrylate is present in the copolymer. Typically, suitable levelsof oxyalkylene-containing (meth)acrylate in the hard phase copolymerwill be from 0.5 to 10% by weight or from 1 to 8% by weight.

In one embodiment of the present invention, the copolymer present in thehard phase is a copolymer of one or more alkyl (meth)acrylates (e.g., amixture of butyl acrylate and methyl methacrylate), methacrylic acid, awet adhesion monomer such as hydroxyethyl ethylene urea methacrylate(HEEUMA), and an oxyalkylene-containing (meth)acrylate in accordancewith Formula (I) or (II), with the relative proportions being selectedso as to provide a Tg within the range of from 0° C. to 100° C. Forexample, the hard phase copolymer may be a copolymer of 35-45% by weightbutyl acrylate, 45-55% by weight methyl methacrylate, 2-6% by weightmethacrylic acid, 1-8% by weight wet adhesion monomer, and 1-8% byweight monomer of Formula (I) or Formula (II), the total equaling 100%.

In another embodiment, the polymer present in the soft phase is acopolymer of butyl acrylate and methyl methacrylate, with the relativeproportions of these monomers being selected so as to provide a Tg ofless than 0° C. which is at least 20° C. lower than the Tg of thecopolymer present in the hard phase. For example, the soft phasecopolymer may be a copolymer of 50-65% by weight butyl acrylate and35-50% by weight methyl methacrylate, the total equaling 100%.

In a typical two stage process, the monomers for either the hard or softpolymer phase are emulsion polymerized to an average particle size of(for example) 25-150 nm, after which the monomer charge for the otherpolymer phase is introduced into the polymerization medium andpolymerized in the presence of the first phase polymer particles to thedesired average final particle size, e.g., less than 350 nm. As is wellknown in the art, control of latex particle size can be accomplished bya variety of techniques, any of which may be applied to the multi-stagepolymerization.

The polymerization of the first polymer phase can be accomplished byknown procedures for polymerization in aqueous emulsion. The monomer orcomonomers to be employed in the preparation of the first domain polymerparticles are dispersed into water with agitation sufficient to emulsifythe mixture. The aqueous medium may also contain a free radicalpolymerization catalyst, an emulsifying agent (i.e., surfactant), orother ingredients that are known and conventionally employed in the artas emulsion polymerization aids.

Catalysts which may be used to cause free radical polymerization includethermal initiators as well as redox initiator systems composed of anoxidizing agent and a reducing agent. Suitable free radicalpolymerization catalysts are the catalysts known to promote emulsionpolymerization and include water-soluble oxidizing agents, such as,organic peroxides (e.g., t-butyl hydroperoxide, cumene hydroperoxide,etc.), inorganic oxidizing agents (e.g., hydrogen peroxide, potassiumpersulfate, sodium persulfate, ammonium persulfate, etc.) and thosecatalysts that are activated in the water phase by a water-solublereducing agent. Such catalysts are employed in a catalytic amountsufficient to cause polymerization. As a general rule, a catalyticamount ranges from about 0.01% to 5% by weight based upon the totalmonomers to be polymerized. As alternatives to heat or catalyticcompounds to activate the polymerization, other free radical producingmeans, such as exposure to activating radiation, can be employed.

Suitable emulsifying agents include anionic, cationic, and nonionicemulsifiers customarily used in emulsion polymerization. Usually, atleast one anionic emulsifier is utilized and one or more nonionicemulsifiers may also be utilized. Representative anionic emulsifiers arethe alkyl aryl sulfonates, alkali metal alkyl sulfates, the sulfonatedalkyl esters, and fatty acid soaps. Specific examples include sodiumdodecylbenzene sulfonate, sodium butylnaphthalene sulfonate, sodiumlauryl sulfate, disodium dodecyl diphenyl ether disulfonate, N-octadecyldisodium sulfosuccinate and dioctyl sodium sulfosuccinate. Theemulsifying agents are employed in amounts to achieve adequateemulsification and to provide desired particle size and particle sizedistribution.

Other ingredients known in the art to be useful for various specificpurposes in emulsion polymerization, such as bases, acids, salts, chaintransfer agents, and chelating agents, can also be employed in thepreparation of the polymer. In one embodiment of the invention, wherethe first stage forms the hard phase polymer and the second stage formsthe soft phase polymer, the second stage polymerization is carried outfollowing the neutralization of the first phase by a base such as sodiumhydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate,sodium bicarbonate.

The monomers in each stage of the multi-stage polymerization may beadded neat or as an emulsion in water. The manner of combining thepolymerization ingredients can be by various known monomer feed methods,such as continuous monomer addition, incremental monomer addition, oraddition in a single charge of the entire amount of monomers. The entireamount of the aqueous medium with polymerization additives can bepresent in the polymerization vessel before introduction of themonomers, or alternatively, the aqueous medium, or a portion of it, canbe added continuously or incrementally during the course of thepolymerization.

Polymerization to form the first polymer phase particles is generallyinitiated by heating the emulsified mixture with continued agitation toa temperature usually between 50 and 110° C., or between 60 and 100° C.Polymerization is continued by maintaining the emulsified mixture at theselected temperature until the desired degree of conversion of themonomer or monomers to polymer has been reached.

Following the polymerization to form the first domain polymer particles,the latex may be filtered to remove any precoagulum and then stabilizedfor storage (pending subsequent use as the dispersed first domainparticles in the second stage polymerization) by the addition of a smallamount of known stabilizer surfactant. In one embodiment, the filteringand intermediate stabilization steps for the first polymer latex areeliminated by proceeding directly to the polymerization of the monomersfor the second polymer phase. The monomers for the second polymer phaseare dispersed with agitation into the aqueous medium containing thefirst polymer phase particles and polymerized with continued agitationin generally the same manner and with the same optional polymerizationaids as described for the preparation of the first polymer phaseparticles. The second polymer phase monomers may be pre-emulsified inwater before being combined with the aqueous medium containing the firstpolymer phase particles. Additional quantities of one or more freeradical polymerization catalysts may be added at the same time themonomers for the second polymer phase are introduced. Heating is carriedout for a time effective to achieve the desired extent of monomerconversion of the second polymer phase.

Following polymerization, the solids content of the resulting aqueousheterogeneous polymer latex can be adjusted to the level desired by theaddition of water or by the removal of water by distillation. Generally,the desired level of polymeric solids content is from about 20%-65% orfrom about 45%-60% by weight on a total weight basis.

Suitable particle sizes can generally be achieved directly from thepolymerization. However, screening of the resulting latex to removeparticles outside the desired size range and to thus narrow the particlesize distribution may be employed. Other techniques such as high shearmixing, grinding, milling, homogenization and the like may also beemployed to modify the particle size or particle size distribution, ifso desired.

The polymer emulsion thereby obtained is useful as a binder component informulating latex coating compositions such as paints and the like.Typically, the polymer emulsion is utilized in a latex coatingcomposition in an amount of from 5 to 90% by weight. The content ofmultiphase emulsion polymer in a latex coating composition (calculatedon a dry solids basis) typically is from 20 to 75% by weight.

For various applications, it is sometimes desirable to have smallamounts of additives, such as surfactants, dispersants, thickeners,bactericides, pH modifiers, and antifoamers, incorporated in the latexcoating composition. This may be done in a conventional manner and atany convenient point in the preparation of the latex coatingcompositions.

The latex coating compositions of the invention may include less than 2%by weight or less than 1.0% by weight of volatile anti-freeze agentsbased on the total weight of the aqueous coating composition. In anotherembodiment, the latex coating compositions are substantially free ofvolatile anti-freeze agents.

The latex coating composition may include at least one pigment. The term“pigment” as used herein includes non-film-forming solids such aspigments, extenders, and fillers. The at least one pigment may, forexample, be selected from the group consisting of TiO₂ (in both anastaseand rutile forms), clay (aluminum silicate), CaCO₃ (in both ground andprecipitated forms), aluminum oxide, silicon dioxide, magnesium oxide,talc (magnesium silicate), barytes (barium sulfate), zinc oxide, zincsulfite, sodium oxide, potassium oxide and mixtures thereof. Typically,the at least one pigment includes at least one of TiO₂, CaCO₃ or clay.Generally, the mean particle sizes of the pigments may range from about0.01 to about 50 microns. For example, TiO₂ particles used in the latexcoating composition may have a mean particle size of from about 0.15 toabout 0.40 microns. The pigment can be added to the latex coatingcomposition as a powder or in slurry form. The pigment is typicallypresent in the final formulated coating composition in an amount fromabout 5 to about 50 percent by weight, more typically from about 10 toabout 40 percent by weight.

The coating composition can optionally contain additives such as one ormore film-forming aids or coalescing agents. Suitable film-forming aidsor coalescing agents include plasticizers and drying retarders such ashigh boiling point polar solvents. Other conventional coating additivessuch as, for example, dispersants, additional surfactants (i.e. wettingagents), rheology modifiers, defoamers, thickeners, biocides,mildewcides, colorants such as colored pigments and dyes, waxes,perfumes, co-solvents, pH adjustment agents (e.g., acids, bases) and thelike, can also be used in accordance with the invention. These additivesare typically present in the latex coating composition in an amount from0 to about 15% by weight, more typically from about 1 to about 10% byweight, based on the total weight of the coating composition. In oneembodiment of the invention, the latex coating composition containslittle or no volatile coalescing agent or volatile film-forming agent(e.g., <0.5% by weight or <0.1% by weight).

As mentioned above, the latex coating composition in some embodimentscan include less than 2.0% of anti-freeze agents based on the totalweight of the aqueous coating composition. Exemplary anti-freeze agentsinclude ethylene glycol, diethylene glycol, propylene glycol, glycerol(1,2,3-trihydroxypropane), ethanol, methanol, 1-methoxy-2-propanol,2-amino-2-methyl-1-propanol, and FTS-365 (a freeze-thaw stabilizer fromInovachem Specialty Chemicals). More typically, the latex coatingcomposition includes less than 1.0% or is substantially free (e.g.,includes less than 0.1%) of anti-freeze agents. Accordingly, the aqueouscoating composition of the invention typically has a VOC level of lessthan about 100 g/L and more typically less than or equal to about 50g/L. Despite the fact that the latex coating compositions of theinvention include little or no volatile anti-freeze agents, thecompositions are capable of possessing freeze-thaw stabilities at levelsdesirable in the art.

The balance of the latex coating composition of the invention may bewater. Although much of the water is present in the polymer latex binderand in other components of the aqueous coating composition, water isgenerally also added separately to the latex coating composition.Typically, the latex coating composition includes from about 10% toabout 85% by weight and more typically from about 35% to about 80% byweight water. Stated differently, the total solids content of the latexcoating composition is typically from about 15% to about 90% or fromabout 20% to about 65%.

The coating compositions are typically formulated such that the driedcoatings comprise at least 10% by volume of dry polymer solids, andadditionally 5 to 90% by volume of non-polymeric solids in the form ofpigments. The dried coatings can also include additives such asplasticizers, dispersants, surfactants, rheology modifiers, defoamers,biocides, mildewcides, colorants, waxes, and the like, that do notevaporate upon drying of the coating composition.

The latex coating compositions of the present invention are typically inthe form of stable fluids that can be applied to a wide variety ofmaterials such as, for example, metal, wood, paper, cardboard,composites, plastics, concrete, glass, ceramics, plaster, dry wall,other coatings, cloth, foams, and the like. The substrate may have beenpreviously painted, primed, undercoated, sanded, conversion coated,oxidized, chemically treated, etched, or the like. The coatingcomposition may be applied to the material or substrate by any suitablemethod such as, for example, dipping, brushing, spraying, rollercoating, knife coating, or the like. Typically, a thin uniform layer(film) of the coating composition is formed on the substrate surface andthen dried to form a dry coating. Drying may be accelerated by heating,if so desired. Multiple dry coating layers may be formed by applyingsuccessive layers of the coating composition. The latex binders of thepresent invention are suitable for use in a wide range of both interiorand exterior zero to low VOC paints from gloss to flat.

The coating compositions of the invention may also be readily adaptedfor use in pressure sensitive adhesives, caulks and sealants, inaddition to paints.

EXAMPLES

Characterization Methods:

Freeze-thaw stability (modified ASTM D2243-82): 1) Fill half pint canstwo-thirds full with paint; Measure and record initial KU viscosity; 2)Cans are placed in freezer at 0° F. for 16˜18 hours and then thawed atroom temperature for 24 hours; KU viscosity is measured if the paintsappear to be fluid; 3) Step 2 and 3 are repeated 5 times or the paint iscoagulated irreversibly.

Low temperature coalescence (LTC): The drawdown films were prepared onLeneta 1B Opacity Charts using 10-mil bird applicator for LTC. The paintfilms were placed in a 40° F. refrigerator immediately after the filmswere drawn down and allowed to dry for 24 hours. The dried films wereexamined for continuity. The degree of cracking on the sealed andunsealed portions was rated on a 1 to 5 scale as follows:

1=severe cracking

2=moderate cracking

3=some cracking

4=slight cracking

5=no cracking

Block resistance: The test paints were prepared on Leneta 1B opacitycharts using a 3-mil bird drawdown bar. The films for room temperature(RT) block were dried in a constant temperature and humidityenvironmental chamber for 1 day. Two square strips measuring 2.54cm×2.54 cm were placed together with paint film against paint film undera 454-gram weight. After 24 hours, the strips were separated andevaluated according to ASTM D-4946 ratings. For the elevated temperature(ET) block test, the paint strips after 1-day drying at CT/CH wereplaced in a 120° F. oven for 30 minutes. The weight load of 1000 gramwas transferred to the paint films via a 2.54 cm diameter rubberstopper. The films were allowed to cool for 30 minutes before the blockratings were given. Room and elevated temperature block were rated onthe ASTM D-4946 scale from 0 (worst) to 10 (best). The test was run intriplicate and the average value was reported.

Polymer Latex Binders and Process

Comparative Example 1

450 parts of deionized water, 1.8 parts of sodium carbonate, and 39.4parts of sodium lauryl sulfate (SLS, 30% in water) were charged into areactor equipped with a paddle stirrer, reflux condensers,thermocouples, and stainless steel feed lines. When the reactor washeated to 85° C., 2.8 parts of sodium persulfate solution in 35.0 partswater was added thereto. The hard phase monomer mixture (calculated Tg˜20° C. using the Fox equation) consisting of 220 parts water, 7.9 partsSLS, 173.7 parts butyl acrylate (BA), 211.5 parts methyl methacrylate(MMA), 18.0 parts methacrylic acid (MAA), and 24.0 parts hydroxyethylethylene urea methacrylate (HEEUMA, 50% in water) was pre-emulsified bystirring in a separate container and then added continuously to thereactor for 1 hour. After 10 minutes of starting the hard phase monomerfeed, the addition of a sodium carbonate (5.1 parts) solution was begun,16.3% of which was fed over 50 minutes and the remainder added over 5minutes. The first stage polymer reaction mixture was then held at 87°C. for 15 minutes. At the end of the hold, the pre-emulsified soft phasemonomer mixture consisting of 123.0 parts water, 433.0 parts BA, 335.0parts MMA, and 4.0 parts SLS was polymerized at 80° C. in the presenceof the first stage composition. 2.8 parts of sodium persulfate solutionwere added simultaneously for 150 minutes. The reactor contents werethen held at 80° C. for 30 minutes. To reduce the residual monomerconcentrations, 0.9 parts of tertiary-butyl hydroperoxide (tBHP) and 1.4parts of sodium metabisulfite (SMBS) were fed over 30 minutes at 80° C.The solids content of the resulting polymer latex binder was 50.8% andthe average particle size was 72 nm.

Example 1

Example 1 (in accordance with the present invention) was preparedfollowing the procedure described in Comparative Example 1 except that12.0 parts of PEGMA 526 (polyethylene glycol methacrylate from Aldrich)was added to the hard phase monomer composition. The solids content ofthe polymer latex binder was 51.3% and the average particle size was 78nm.

Example 2

Example 2 (in accordance with the present invention) was preparedfollowing the procedure described in Comparative Example 1 except that12.0 parts of Sipomer PAM200 (from Rhodia) was added to the hard phasemonomer composition. The solids content of the polymer latex binder was50.5% and the average particle size was 77 nm.

The polymer latex binder compositions of Comparative Example, Example 1and Example 2 were formulated into low VOC latex coating compositionsusing the various additional components listed in Table 1. Table 2 showsthe properties of the latex coating compositions.

TABLE 1 Low VOC Latex Coating Composition Density Mass Vol lbs/gallon(lbs) (Gallons) Common Grind Water 8.33 32.0 3.8 Proxel ® GXLpreservative 9.4129 1.5 0.2 BYK ® 025 defoamer 8.34 0.5 0.1 Tamol ® 1124dispersant 9.9 20.0 2.0 Ammonia (28%) 7.7 4.0 0.5 Ti-Pure ® R-706 TiO₂33.3 210.0 6.3 Water 8.33 50.0 6.0 Total Grind 318.0 18.9 LetdownPolymer latex binder 8.85 580.0 65.5 BYK ® 025 defoamer 8.34 2.0 0.2Rheolate ® 278 thickener 8.58 4.5 0.5 Water 8.33 124.0 14.9 Total Paint1028.5 100.1

TABLE 2 CE1 E1 E2 Equilibrated 103 104 98 KU Low Temperature sealed 5 53 Coalescence scale 1-5, 5 = best unsealed 5 5 2 Block Resistance 1d-RT8 8 8 1d-ET 5 5 3 Freeze thaw FT cycles failed 5 5 KU change >40 9 8after 5 FT cycles

What is claimed is:
 1. A multiphase emulsion polymer for coatingcompositions, said multiphase emulsion polymer comprising at least onehard phase polymer having a glass transition temperature of from 0 to100° C. and at least one soft phase polymer having a glass transitiontemperature at least 20° C. lower to no more than 100° C. lower than theglass transition temperature of the hard phase polymer using the Foxequation, wherein the hard phase polymer is a copolymer of one or moreethylenically unsaturated monomer, and one or moreoxyalkylene-containing (meth)acrylate corresponding to formula (I) or(II) or a mixture thereof:CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—R²;  (I)CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—P(═O)(OY)₂;  (II) wherein R¹ is H or CH₃, R²is H or a C₁-C₈ alkyl group, each X is independently —(CH₂)₂—,—CH₂CH(CH₃)— or —CH(CH₃)CH₂—, each Y is independently H, ammonium or analkali metal atom, and n is an integer of from 1 to 30, wherein the softphase polymer is a copolymer of monomers selected from the groupconsisting of C1-C18 alkyl(meth)acrylates, halo- and hydroxylsubstituted alkyl esters of (meth)acrylic acid, vinyl esters of linearand branched carboxylic acids having 2 to 20 carbon atoms, unsaturatedC3-C6 monocarboxylic acids, monoesters of unsaturated C4-C6 dicarboxylicacids, unsaturated C4-C6 dicarboxylic acids, (meth)acrylonitrile,cycloalkyl(meth)acrylates, aryl and alkaryl esters of (meth)acrylates,acetoacetate-containing acrylate monomers, olefins, and dienes, whereinthe at least one hard polymer phase is formed as a first stage polymerand the at least one soft polymer phase is subsequently polymerized inthe presence of the first stage polymer, wherein the multiphase emulsionpolymer is in the form of latex particles and wherein the latexparticles comprise an inner phase comprised of the soft phase polymerand an outer phase comprised of the hard phase polymer, and wherein themultiphase emulsion polymer is in the form of latex particles having anaverage particle size of less than 200 nm.
 2. The multiphase emulsionpolymer of claim 1, wherein the at least one ethylenically unsaturatedmonomer is a mixture of at least one alkyl (meth)acrylate, methacrylicacid and at least one wet adhesion monomer.
 3. The multiphase emulsionpolymer of claim 1, wherein the at least one ethylenically unsaturatedmonomer is a mixture of butyl acrylate, methyl methacrylate, methacrylicacid and hydroxyethyl ethylene urea methacrylate.
 4. The multiphaseemulsion polymer of claim 1, wherein the hard phase polymer is acopolymer is comprised of 0.5 to 10% by weight of oxyalkylene-containing(meth)acrylate.
 5. The multiphase emulsion polymer of claim 1, whereinthe oxyalkylene-containing (meth)acrylate is a polyethylene glycolmethacrylate.
 6. The multiphase emulsion polymer of claim 1, wherein theoxyalkylene-containing (meth)acrylate is a phosphate ester of apolyethylene glycol methacrylate.
 7. The multiphase emulsion polymer ofclaim 1, wherein the multiphase emulsion polymer is in the form of latexparticles having an average particle size of less than 150 nm.
 8. Themultiphase emulsion polymer of claim 1, wherein the soft phase polymeris a copolymer of C1-C18 alkyl (meth)acrylates.
 9. The multiphaseemulsion polymer of claim 1, wherein the soft phase polymer is acopolymer of butyl acrylate and methyl methacrylate.
 10. The multiphaseemulsion polymer of claim 1, wherein the soft polymer phase representsfrom 90% to 40% by weight of the multiphase emulsion polymer and thehard polymer phase represents from 10% to 60% by weight of themultiphase emulsion polymer, the total weight amount of soft polymerphase and hard polymer phase equaling 100%.
 11. A method of making apolymer latex binder for coating compositions, comprising: (a)copolymerizing an aqueous multiphase emulsion of one or moreethylenically unsaturated monomer, and one or moreoxyalkylene-containing (meth)acrylate corresponding to formula (I) or(II) or a mixture thereof:CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—R²;  (I)CH₂═C(R¹)—C(═O)—O—[X—O]_(n)—P(═O)(OY)₂;  (II) wherein R¹ is H or CH₃, R²is H or a C₁-C₈ alkyl group, each X is independently —(CH₂)₂—,—CH₂CH(CH₃)— or —CH(CH₃)CH₂—, each Y is independently H, ammonium or analkali metal atom, and n is an integer of from 1 to 30, to form a hardphase polymer having a glass transition temperature of from 0 to 100°C.; (b) polymerizing one or more additional monomers in the presence ofthe hard phase polymer to form a soft phase polymer; wherein the softphase polymer is a copolymer of monomers selected from the groupconsisting of C1-C18 alkyl(meth)acrylates, halo- and hydroxylsubstituted alkyl esters of (meth)acrylic acid, vinyl esters of linearand branched carboxylic acids having 2 to 20 carbon atoms, unsaturatedC3-C6 monocarboxylic acids, monoesters of unsaturated C4-C6 dicarboxylicacids, unsaturated C4-C6 dicarboxylic acids, (meth)acrylonitrile,cycloalkyl(meth)acrylates, aryl and alkaryl esters of (meth)acrylates,acetoacetate-containing acrylate monomers, olefins, and dienes, whereinthe hard phase polymer has a glass transition temperature of from 0 to100° C. and the soft phase polymer has a glass transition temperature atleast 20 to 100° C. lower than the glass transition temperature of thehard phase polymer; wherein the emulsion polymer is in the form of latexparticles having an average particle size of less than 200 nm, andwherein the latex particles comprise an outer phase comprised of thehard polymer phase and an inner phase comprised of the soft polymerphase.
 12. The method of claim 11, wherein the at least oneethylenically unsaturated monomer is a mixture of at least one alkyl(meth)acrylate, methacrylic acid and at least one wet adhesion monomer.13. The method of claim 11, wherein the at least one ethylenicallyunsaturated monomer is a mixture of butyl acrylate, methyl methacrylate,methacrylic acid and hydroxyethyl ethylene urea methacrylate.
 14. Themethod of claim 11, wherein the hard phase is a copolymer comprised of0.5 to 10% by weight of oxyalkylene-containing (meth)acrylate.
 15. Themethod of claim 11, wherein the oxyalkylene-containing (meth)acrylate isa polyethylene glycol methacrylate.
 16. The method of claim 11, whereinthe oxyalkylene-containing (meth)acrylate is a phosphate ester of apolyethylene glycol methacrylate.
 17. The method of claim 11, whereinthe soft phase polymer is a copolymer of C1-C18 alkyl (meth)acrylates.18. The method of claim 11, wherein the soft phase polymer is acopolymer of butyl acrylate and methyl methacrylate.
 19. The method ofclaim 11, wherein the soft polymer phase represents from 90% to 40% byweight of the multiphase emulsion polymer and the hard polymer phaserepresents from 10% to 60% by weight of the multiphase emulsion polymer,the total weight amount of soft polymer phase and hard polymer phaseequaling 100%.